Gluconic acid salts of certain oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



United States Patent GLUCONIC ACID SALTS OF CERTAIN OXYALKYL- ATED AMINE MODIFIED THERMOPLASTIC PHENOL-ALDEHY DE RESINS, AND METHOD -OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application January 26, 1953, Se-

rial No. 333,389, now Patent No. 2,771,448, dated November 20, 1956. Divided and this application April 9, 1956, Serial No. 576,825

13 Claims. (Cl. 260-53) My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the waterin-oil type and particularly petroleum emulsions. My invention is also concerned with theapplication of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

7 My aforementioned copending application, Serial No. 301,806, filed July 30, 1952, is concerned with the process of first condensing certain phenol'aldehyde resins, therein described in detail, with certain basic hydroxylated polyamines, therein described in detail, and formaldehyde, which condensation is followed by oxyalkylation with certain monoepoxides, also therein described in detail.

. The present invention is concerned with the aforementioned oxyalkylated amino resin condensate in the form of a gluconic acid salt, i. e., a form in which part or all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt ofgluconic acid.

My aforementioned co-pending application, Serial No. 310,554, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including the amine resin condensates described in the aforementioned application Serial No. 301,806.

Needless to say, all that is required is to prepare the amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368 dated March 7, 1950, to

R 2,839,503 Patented June. 17,

De Groote et al. In said patent such test for emulsifica-l tion using a water-insoluble solvent, generally xylene, is described as an index of surface activity. 1

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent s such as ethylene glycol diethylether, or.

a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there, will be two phases on Vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of Xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondary polyamines which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, thehydroxylated polyamine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation;

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding, in the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previa ously described chemical compounds or reaction prod: ucts'in the form of gluconic acid salts; and

Part 8 is concerned with uses for the products herein described, either as such or after modificatiomincluding any applications other than those involving resolution of petroleum emulsions of the water-in-oil type. This part is limited also to the use of the gluconic acid salts.

For reasons which are obvious, particularly for convenience and ease of comparison, the various parts are in substantially verbatim form as they appear in one or more of the aforementioned co-pending applications, to wit, Serial Nos. 288,745, 296,086, 301,806, 310,554, and 329,485. For example, Parts 1, 2, 3 and 4 are substantially as they appear in co-pending application, Serial No. 329,485, filed January 2, 1953; Part 5 is substantially the same as it appears in aforementioned co-pending application, Serial No. 301,806, filed July 30, 1952, and Serial No. 310,554, filed September 19, 1952. Part 6 corresponds approximately to what appears in Serial No, 329,485, filed January 2, 1953.

PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of de rivatives of heat-stable and oxyalkylation-susceptible resinous condensation products obtained by oxyalkylating the amine resin condensates described in applications Serial Nos. 288,745 and 296,086 to which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in :part, be an over-simplificationin an effort to present certain resin structure. Such formula would be the following:

R n R in which 'R represents an aliphatic hydrocarbon substituent generally having 4 and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small Whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is 'derived from a hydroxylated basic polyamine and usually a strongly basic polyamine having at least one secondary amino radical and free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be indicated thus:

inwhich R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical, and with the further proviso that there be present at least one hydroxylated hydrocarbon radical such as a hydroxyl alkyl radical, a hydroxy alicyclic radical, a hydroxy alkylaryl radical, etc. Such hydroxylated radical need not be limited to a single hydroxyl group as in the case 'of an alkanol radical but may include 2 or more hydroxyl groups, such as a sglycerol derivative or, in essence, a dihydroxy propyl group.

Actually, what has been depicted in the formula above is only an rover-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to oxyalkylated derivatives obtained by the oxyethylation or oxypropylation, for example, of substituted poly-alkylene amines of thefollowing structure:

in which R' has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176 dated July 22, 1941, to Blair. Reaction with an alkylene oxide, such as ethylene oxide or propylene oxide must of course be sure that the derivative so obtained still has at least one secondary amino hydrogen group, all of which will be illustrated by numerous examples susbsequently.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al., which describes alkylene diamines and polymethylene diamines having the formula where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as '1 to 8. Such compound as the one just described can be reacted with a single mole of ethylene oxide or propylene oxide or glycide to give a suitable reactant. A further limitation in light of the required basicit is that the-secondary amino radical shall not be directly joined to an aryl radical or 'acyl radical or some other negative radical. Needless to say, What has been stated above in regard to the groups attached to nitrogen is not intended to exclude an oxygen-interrupted carbon atom linkage :or aringilinkage .as in the instance of compounds obtained by converting an N-aminoalky'lmorpholine of the formula wherein n is a whole number from 2 to 12 inclusive, and the-nitrogen atoms are separated by at least two carbon atoms, into a secondary amine by means of an 'alkylene oxide, such as ethylene oxide, propylene oxide, or glycide, so as to yield acompound such as carom n o )N-CJlM-N 'OHrCHt .0 21140351 The introduction of two such'hydroxylated polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of Ways. In the first place, a'basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical'R', there may be a counter-balancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the 'hydrophile effect of the nitrogen atom. Finally, in such cases where -R' contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect. In the present'procedure the polyamino reactant invariably has at least one hydroxyl group and also may have a reoccurring ether linkage, all of which inturn affects the hydrophile properties.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical'in the ortho or para position, i. e., the uphenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which arere'active to formaldehyde, i. e., they are difunctional from the standpoint of "rnethylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates :that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifun'ctional radical, or 'in'terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or a. during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from, an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heatstable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation', under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is noobjection to the employing of a temperature above the boiling point of water. As a matter of fact, all-the examples included subsequently employ temperatures going up to 140 to 150 C. What is said above deserves further amplification at this point for the reason that it may shortenwhat is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, forexample) it is necessary tohave manufacturing procedure which will allow reactions totake place at the'interface of the two immiscible liquids', to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion eX-, cept by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e:. somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to

the procedure employed in the process is not intended to' limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic'catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the.

amine so as to introduce a methylol group attachedtov nitrogen which, in turn, would reactwiththe resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three difierent molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH on on H I; i 0 o n H In the above formulan represents a small whole number varying from 1 to 6, 7.01 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n. varies from 1 to 4; R represents an aliphatic hydroearbonsubstituent, generally an 'alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resin herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin withtwo'moles of formaldehyde and two moles of a basic non-hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus;

man:

R R n R The basic polyamine may be designated thus:

RI HN/ stituted imidazoline radical or a substituted tetrahydro:

pyrimidine radical, with the proviso that there must be present at least one hydroxyl radical .as part .of at least one of the occurrences of R. However, if one attempts to incorporate into the formula a structure such as an oxyethylated or oxypropylated derivative of a substituted polyalkylene amine of the following type:

in which the various characters have the same significance as in initial presentation of this formula, then one becomes involved in added difficulties in presenting an overall picture. Thus, for sake of simplicity, the hydroxylated polyamine will be depicted as R! HN subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, it at all, 2 resin units may combine without any amine in the reaction products, as indicated in the following formulas:

n I R R n As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

having neither acid nor basic properties in the ordinary sense or without any-catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of :a free base. The amount may be as small as a 200th of a percent and as much as'a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular Weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resinsI found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized :in the following table:

TABLE I M01. wt Ex- Position R oi resin ample R of R derived n molecule number 0m (based on n+2) Phenyl Farah-.. Formal- 3. 992.5

Tertiary butyl 3. B82. 5 Secondary but 3. 882. 5 Cyclo-hexyl. 3. 1, 025. Tertiary amyl 3. 959. Mixed secondary 3. 805. and tertiary amyl.

3. 805. 3. 1,036. 3. 1, a. '1, 3. 1, d yl 3. 1, Tertiary butyl 3,

Tertiary arnyl 3,

Nonyl. 3.

Tertiary butyl 3 17a Tertiary amyl 3,

N onyl 3. 4

Tertiary butyl 3 Tertiary amyl 3. Non B. 3 Tertiary butyL 4. 996.

Tertiary amyl. 4. 1,083. Non '4. 1,480. Tertiary butyl 4. 1, 094. Tertiary amyl... 4. 1, 189. Nonyl 4. '1, 570. Tertiary 'amyl. 1. 604. Cyclo-hexyL. 1. 646. Hex "110.-. undo 1. 653. o do Acetalde- 1. 688.

hyde. do 1. 786.0 1. 835. 0 2. 986. 0

PART 3 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polyarnine and preferably a strongly basic polyamine having at least one secondary amino radical, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetra hydropyrirnidine' groups, in which the hydrocarbon radicals present whether monovalent or divalent are alkyl, alkycyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxyalkylation of low cost polyamines. The cheape'st'amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the casof polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of example the following formulas are included. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

H0 UREA CHLOH (H O CgHt) :NCzHrgO IHIN (CIH(OH)2 H0 CsHl GBHIOH CH: CH;

Nciarocinm HO (31H; CiHiOH CHI H CH: NpropyleneNpropyleneN HOClHA CsHeOB CHa\ I NCQHANCQHJNCIHINOiHQN H H H HO CzHa Another procedure for producing suitable polyamine's' is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide; propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with, an imine and then the use, of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide. 7

Reactions involving the same reactants previously, described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles ofan alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation, reaction. In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite, hydrophile effect by virtue of the ether linkage. Suitable polyether amines susceptible to conversion in the manner described include those of the formula in which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to 1, with the proviso that the sum of m plus m' equals 2; and R has its prior significance, particularly as a hydrocarbon radical. The preparation of such amineshas been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943 to Hester, and 2,355,337 dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as 021150 C H4O CgHrO 0211 0 CzHrCl Such haloalkyl ethers can react with ammonia, or with a primary-amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines. so obtained and suitable for conversion into appropriate polyamines are exemplified by (CH OCH CH,CH CH CH CH NH. Z Other similar secondary monoamines equally suitable for such conversionreactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659 dated May '8, 1945, to Jones et al. In the above formula R may be methyl, ethy, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter,

amines ofthe kind described in U. S. Patent No. 2,482,546

dated September 20, 1949, to Kaszuba, provided there is'no negative group or halogen attached to the phenolic nucleus. Examples include the following: betaphenoxy ethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as H Npro pyleneNpropyleneN C 2H4 H N CIH-iNCZHANOZH4 Z 4 H H H H O C 7H4 1114 O H In the first of the two above formulas if the reaction involves a terminal amino'hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took'placc at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above,although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on Whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group If there. are two points of reactivity towards formaldehyde as illustrated by theabove examples .it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a a 12 large variety of compounds might be obtained due to Such multiplicity of reactive radicals. This can be illustrated by the following'tormula:

Certain hydroxylated 'polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

C HaNH C H:

C-HaNHCHPO C H: 0-H

C HaNH 0 Hi CHz-CH;

HC-OH CHr-CH;

HO-CH CzHaOH As is well known one can prepare ether amino alcohols of the type RO-CH2CH (OH) CHaNHCHzCHzNHCHzCH( OH) CHe-OR in which R represents an alkyl group varying from methyl to normal decyl, and in fact, the group may contain as many as 15, 20 or even 30 carbon atoms. See J. Org. Chem, 17, 2(152).

Over and above the specific examples which have appeared previously, attention is directed to the fact that a number of suitable amines are included in subsequent Table 11.

PART 4 I The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since theresin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,745 and 296,086, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1 b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to the average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added in a little over 3 hours. The mntture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part of the xylene which was removed until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to'40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both thesolution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this precedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reaction Max. Ex. No. Resin Amt., Amine used and formaldehyde Solvent used and Reaction time, distill. used grs. amount soln. and amt. amt. temp, "0 hrs. tegrp Xylene, 500 g 21-24 24 150 Xylene, 480 g. 20-23 27 156 Xylene, 610 g. 22-27 25 142 20-25 28 145 23-27 34 150 25-27 30 152 23-26 38 141 20-21 25 143 23-24 25 140 22-25 '25 148 20-21 25 158 21-25 28 152 22-24 26 143 .do .-d0 25-27 36 144 ..do Xylene, 500 gm... 26-27 34 141 Xylene, 400 g 21-23 25 153 do. do 20-22 28 150 Xylene, 500 g 23-25 27 155 do Xylene, 400 g. 20-21 34 150 o Xylene, 450 g. 20-24 36 152 Amine H, 221 g do Xylene, 500 g. 20-22 30 148 do "do-.- Xylene, 400 g 20-29 24 143 Amine I, 172 g do Xylene, 450 g 20-22 32 151 391 Amine I, 86 g 30%, 50 g Xylene, 300 g 20-26 36 147 15 As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

HO CHzCHgNH- Hg Amine H CHsNHCH CHQNHCHFCHzQH CHaNHCHz PART In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids .are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner. The oxyalkylation of the amine resin condensates is carried out by procedures which are commonly used for the oxyalkylation of oxyalkylation susceptible materials. The factors to be considered are discussed in some detail in applications Serial Nos. 301,806 and 310,554 and reference is made to those applications Amine I for a description of suitable equipment, precautions to be taken and a general discussion of operating technique.

The following examples are given by way of illustration.

Example 10 The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate 1b was in turn obtained from symmetrical di(hydroxyethyl)ethylene diamine, previously described for convenience as Amine A, and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from parater tiarybutylphenol and formaldehyde. 12.02 pounds of this resin condensate were dissolved in 5 pounds of solvent (xylene) along with one pound of finely powdered caustic f 16 In some subsequent examples pressures-up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately 1% hours, and then continue stirring for 15 minutes longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 12.02 pounds. This represented a molal ratio of 27.3 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2404. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables IH and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a dilferent oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 1c, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), about 12.02 pounds. The amount of oxide present in the initial step was 12.02 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 12.02 pounds, all addition .of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 24.04 pounds and the molal ratio of ethylene oxide to resin condensate was 54.7 to 1. The theoretical molecular weight was The maximum temperature during the operation was C. to C. The maximum pressure was in the range of 15 to 20 pounds. The time period was a little less than before, to wit, only 45 minutes.

Example 30 The oxyethylation was continued and the amount of oxide added again was 12.02 pounds. There was no added catalyst and no added solvent. The molal ratio of oxide to condensate was 109 to 1. Conditions as far as temperature and pressure. were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2 /2 hours. The theoretical I molecular weight at the endv of the prior step was 4808,

and at the end of this step-6010. The reaction showed some slowing up at this particular stage.

Example 50 The oxyethylation continued with the introduction of another 12.02 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 7212, and the molal ratio of oxide to resin condensate was 136.5 to 1. The time period, however, was slightly less than before, to wit, 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 6c The same procedure was followed as in the previous examples. The amount of oxide added was another 12.02 pounds, bringing the total oxide introduced to 72.12 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 84.14 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 9616. The time required for the oxyethylation was the same as in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 96.16 pounds. The theoretical molecular weight was 10,818. The molal ratio of oxide to resin condensate was 218 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was slightly longer than in the previous step, to wit, 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethyllation was started in a l5-gallon autoclave and then transferred to a -gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 41c through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can 'be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI, it is to be noted that the first column refers to Examples 1c, 20, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by "d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 37c, 40c, 46c, and 770. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 40c were obtained by the use of ethylene oxide, it is obvious that those obtained from 370 and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 46c and 770 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial '0 series such as 370, 40c, 46c, and 770, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second. oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 370, consisting of the reaction product involving 12.02 pounds of the resin condensate, 30.05 pounds of ethylene oxide, 1.0 pound of caustic soda, and 5.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any. l

The

to the The Molee. wt. based oretlcal value ker product oxide on thealkyl.

ompd.

made to obtain colorthemselves may be Condensation of a As far as use in de- Molalratlo Ethl. Propl. oxide to oxyto oxyalkyl. suseept. suscept.

cmpd.

Solvent, lbs.

55555555 0000000022222222000000000000000000000000 5 fiw5 5 iiroimdfmd xmimd d Amididd x kd a iiiiid diiiiflii if xylene, adds nothin or some other industrial uses,

or a combination of both of them.

Oxyalkylation generally tends to yield Composition at end oxide, lyst,

lbs.

h the final color is a lighter amber with a Such products can be decolorized by the Ethl. Propl. Cataoxide, lbs.

st mentioned,

The colors of the products usually vary from a red- Generally speaking, the amount of alkaline catalyst ene oxide is used along with either'one of the two oxides dish amber tint to a definitely red, and amber.

reason is primarily that no effort is less resins initially and the resins yellow, amber, or even dark amber.

nitrogenous product invariably yields a dar than the original resin and usually has a reddish color. The solvent employed,

color but one may use a darker colored aromatic petroleum solvent.

lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in whic reddish tint.

use of clays, bleaching chars, etc.

mulsification is concerned there is no justification for the cost of bleaching the product.

present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid,

for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also.

preferred procedure -is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE III ion If de- Oompositlon before Such distillation also l s I s l s t i s 4 i s I i m 5555555544444444444444444444444455555655 V 000033330000333322229.7770000333300003333 ms ILILLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL W n IIIIIII WMS IX a P0 e 1 22468024 .6284062 .864 O8 6 84069 23 F .ri 246 RWUZ4 Ranmfllfifioo 7 L5 R. Z.Lfiw 357 Lom nu 22 222226666666688 00 00003333333377 88888866666666 2 77777788888888W0WWMM W 2 1 g from these procedures may conempd, cmpd.,

ex. No. lbs.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylat step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular Weight at the end of the initial oxyalkylation step; i. e., oxyethylati'on for 1d through 16d, and oxypropylation for 17! through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resultin tain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. sired the solvent may be removed by distillation, and particularly vacuum distillation. may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain What may be termed an inditferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butyl- Ex. N0.

*0xyalkylation-suseeptible.

TABLE VI Max. Max. Solubility Ex. temp., pres, Time, No. C. p. s. i. hrs.

Water Xylene Kerosene 15-20 1% Insoluble 15-20 Emulsifiable. 15-20 1 15-20 2% 15-20 2 15-20 3 1 15-20 3 15-20 4 15-20 1 15-20 15-20 15-20 3 15-20 3 15-20 3 15-20 4 15-20 5 -15 10-15 10-15 10-15 10-15 10-15 10-15 25-30 25-30 25-30 25-30 .do 10-15 Insoluble 10-15 do 10-15 Emulsifiable. 10-15 d0 10-15 10-15 10-15 10-15 20-25 20-25 20-25 20-25 20-25 20-25 20-25 20-25 -35 Insoluble. 30-35 Do. 30-35 Soluble. 30-35 D0. 30-35 D0. 30-35 Do. 30-35 Do. 30-35 Do. 15-25 Insoluble 15-25 D0. 15-25 Soluble. 15-25 D0. 15-25 Do. 15-25 D0. 15-25 Do. 15-25 D0. 20-25 Insoluble 20-25 Do. 20-25 D0. 20-25 Soluble. 5 20-25 D0. 20-25 D0. 20-25 D0. 20-25 D0. 20-25 Insoluble 20-25 D0. 20-25 D0. 20-25 Do. 20-25 D0..

20-25 Dispersible 20-25 uble. 20-25 D0. 10-15 Insoluble 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Dlsperslble 10-15 D0. 10-15 D0. 10-15 Soluble 10-15 Insoluble 10-15 .1 D0. 10-15 ,do. Do. 10-15 Emulsifiable. Do. 10-15 D0. 10-15 Dispersible. 10-15 D0. 10-15 Soluble. 20-25 Do. 20-25 Do. 20-25 Dispersible. 20-25 Insoluble. 20-25 Do. 20-25 D0. 20-25 d0 do. Do.

Max Max. Solubility Ex. temp pres, Time, No. 0. p. s. 1. hrs.

Water Xylene Kerosene 20-25 '2 Emulsifiable" Insoluble 20-25 Do. 20-25 1 Do. 20-25 1% D0. 20-25 2% D0. 20-25 1 D0. 20-25 1% D0. 20-25 2 D0. 20-25 2% Do.

PART 6 Needless to say, the solvent could have been removed The conversion of the oxyalkylated basic condensate of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the 'basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, if required, is ignored in subsequent Table VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, or at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling'point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuationin-part of certain co-pending applications and reference is made to aforementioned copending application, Serial No. 329,485, filed J an. 2, 1953.

The co-pending application, Serial No. 329,485, filed January 2, 1953, described the neutralization of the non-oxyalkylated condensate.

Reference now is made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculation showing the amount of gluconic acid (50%) required to neutralize a certain amount of condensate; for instance, compare Example le in Table VII with Example 1b in Table II. In any event, since there were available various oxyalkylated derivatives of condensates 1b and 1012, these particular oxyalkylated derivatives were used for the purpose of illustrating salt formations, all of which is illustrated in Table VIII.

Briefly stated, referring to Example he in Table VII it is to be noted that 1202 grams of the nonoxyalkylated condensate required 1570 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1202 grams of the condensate Example lb, when converted into the oxyalkylated derivative as obtained from 2c, were equivalent to 4135 grams. Therefore, 4135 grams were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate ganerally is a liquid and, as a rule, contains a comparatively small amount of solvent. Note the examplesv in Table VIII. The solvent happened to be xylene in this.- instance but could have been benzene, aromatic petroleum solvent, or the like.

from the oxyalkylated derivative by use of vacuum distillation and this is particularly true if benzene happened to be the solvent. The product obtained from oxyalkylation invariably is lighter than theinitial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color, or an amber shade with a reddish tint.

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or aphase-separating trap. If there happened to be any tendency for the product to separate then the solvents having hydrotropic properties, such as the diethylether of ethyleneglycol, or the like, are used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the product is diluted to approximately 50%, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justification for the added cost of decolorization. The salt form can be dehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phase-separating trap.

The product as prepared, without attempting to decolorize, eliminate any residual catalyst in the form of a salt, and without any particular effort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demulsifier for petroleum emulsions of the water-in-oil type, or oil-in-water type; for the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalkylation may be solids but are generally viscous liquids or liquids which are almost solid or tacky. Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to polyglycols, of course depending primarily on the amount.

27 of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in the majority of cases are liquids. Needless to say, if a solvent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and the simplicity of salt formation it does not appear that any illustration is required. However, previous reference has been made to Table VIII. The first example in Table VIII is Example If. The following is more specific data in regard to Example If.

VIII. For convenience, Table VII is included at this point just preceding Table VIII.

TABLE VII Salt formation calculated on Condensate in turn derived from basis of non-oxyalkylated Salt condensate from Salt con- Ex. den- 37% Wt. of N o. sate Amt. Amt. Amine formconden- Theo. 50% glu- No. Resin resin, Solvent sol- Amine used 1 used, aldesate on basic conic N0. gms. vent, gms. hyde, solventnitrogen, acid, gms. gins. freebasis, gins. gins.

' gms.

882 296 2 200 1, 202 56 1, 570 480 148 81 640 28 785 633 148 81 793 28 785 441 176 2 I00 629 28 785 480 176 81 868 28 785 633 176 2 100 851 28 735 882 324 162 1, 230 56 1, 570 480 162 2 100 654 28 785 633 162 2 100 807 28 785 473 256 Z 100 741 28 785 511 256 2 100 779 28 785 665 256 2 100 933 28 785 882 296 2 200 1, 202 28 392 441 176 2 100 629 28 302 882 625 Amine O 324 102 1, 230 28 392 1 For description of amines see notes following Table II. 2 formaldehyde.

TABLE VIII Grams of oxyalky1- ated compound Obtained in turn from Percent which is equiv. percent Oxyalkylcondento grams of congluconic Ex. No. ated desate in densate acid to rivative, oxyalkylneutral- Ex. No. ated deize, grams Conden- Amt. eon- EtO PrO Solvent rivative Oxyalkyl- Condensate, densate, amt., amt., amt., ated comsate Ex. N 0 lbs. lbs. lbs. lbs. pound Example If PART 7 The salt was made from oxyalkylated derivative 20. Oxyalkylated derivative 20, in turn, was made from condensate 1b; condensate 1b was made from resin Example 2a and Amine A, which is symmetrical di(hydroxyethyl)- ethylenediamine. 882 grams of the resin were dissolved in approximately an equal weight of xylene and reacted with 296 grams of the hydroxylated diamine and 200 grams of 30% formaldehyde. All this has been described previously. The weight of the condensate on a solvent-free basis was 1202 grams. This represented approximately 56 grams of basic nitrogen. Referring to Table VIII it will be noted that 12.02 pounds of the condensate were combined with 24.04 pounds of ethylene oxide and 5 pounds of solvent. In any event, 4135 grams of the oxyalkylated derivative 20 were placed in a laboratory de- Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyi alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with convicewhich, although made of metal, was the equivalent of ventional demulsifying agents. Moreover, said material 29 or materials may be used alone or in admixture with other suitable well-knowu classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland Water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of my invention when employed as demulsifying agents.

The materials of my invention, when employed as treat ing or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above. the products herein described may be used not only in diluted form. but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Gluconic acid salt, for example, the product of Example If, 20%;

A cyclohexylamine salt of a lone monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid,24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 8 The gluconic acid salts herein described can be used as emulsifying agents for oils, fats and Waxes; as ingre dieuts in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning vvand mordanting industries. They also can be used for preparing boring or metal cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. Also, the gluconic acid salts are useful in dry cleaners soaps.

Also, they may be used as additives in connection with other emulsifying agents; they may be used to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata and particularly in secondary recovery operations using aqueous flood Waters.

After oxyallcylation a condensate of the kind previouspolypropylated naphthapetroleum solvent,

ly described becomes a derivative which retains basic nitrogen radicals and also includes alkanol radicals such as the hydroxyethyl or hydroxypropyl radical. Thus, in attempting to dehydrate the oxyalkylated salt derivatives from gluconic acid'or merely by heating there may he a rearrangement wherein one forms the ester in the same manner that triethanolamine oleate can be converted into oleyl triethanolamine. Thus the compounds described may serve as precursors for other derivatives obtained by esterification. In fact, any reference to decomposition on heating must of necessity include such possibility.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

l. A three-step manufacturing process including the method of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4, 6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

2. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having 31 at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any aminonitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reactionbeing conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and cxyalkylationsusceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

3. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylcne oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

4. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formalde ryde; said condensation reaction being conducted at a temperature sufficiently high to eliminate'water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reac tion be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be appproximately 1, 2 and 2 respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

5. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, lov. -stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by-reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virture of a formaldehydederive-d methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible; followed by an oxyalkylation step by means of an alpha'beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

6. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyaminc 'be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

7. The manufacturing procedure of claim 1 wherein the oxyalkylati'on step is limited to the use of both ethylene oxide and propylene oxide in combination.

8. The manufacturing procedure of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

9. The manufacturing procedure of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

10. The manufacturing procedure of claim 4 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The manufacturing procedure of claim 5 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

12. The manufacturing procedure of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The product resulting from the three-step manufacturing procedure defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A THREE-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF FIRST CONDENSATING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOULBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLO-FORM ING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 